1. Field of the Invention
This invention relates to a method of oxidatively treating gases, liquids, slurries and surfaces in which high energy oxidants are created through the nebulization of an oxidizer into an energy field. If the media requiring treatment may itself be nebulized, treatment will occur within the radiation/energy field. If the media requiring treatment is a surface or bulk slurry, the energy field is positioned directly above but not on the surface requiring treatment. This oxidation method may be employed for disinfection, purification, sterilization, destruction of organic molecules, oxidation of inorganics, oxidation of metals, and co-precipitation of metals.
2. General Background of the Invention
Free radical formation is a process that has been developed for the purification and disinfection of contaminated liquids, gases, and surfaces. The present invention is an efficient method of free radical application through instantaneous formation of free radicals through the nebulization of liquid and gas oxidants through an energy field.
The process of nebulization or atomization has per se been used in prior art for the dispersion of powders or liquids into clouds (U.S. Pat. No. 4,993,411), humidification of air or oxygen gas for inhalation (U.S. Pat. Nos. 6,511,050; 5,407,604; 4,993,411) the dispersion of fuel into a cloud for efficient combustion (U.S. Pat. Nos. 4,696,719; 4,267,976), and the saturation of a liquid with oxygen, ozone or other gas (U.S. Pat. No. 5,366,696). The dispersion of liquids, slurries or solids into nano-sized droplets or particles increases the effective surface area available for instantaneous reaction and therefore increases efficiency of processes.
Prior art nebulizers which can be used in this process include two examples shown in U.S. Pat. No. 4,344,574 (cross-flow) and U.S. Pat. No. 4,575,605 (concentric), which both atomize a liquid with a gas at high velocity.
Concentric nebulizers have evolved into models with adjustable inner capillary tubes (see for example U.S. Pat. No. 5,884,846), tips with varying geometry (see for example U.S. Pat. No. 6,032,876), direct injection high efficiency models (see for example U.S. Pat. No. 6,166,379), a supersonic nozzle nebulization apparatus (see for example U.S. Pat. No. 6,009,869), a concentric nebulizer with electrospray capability (see for example U.S. Pat. Nos. 6,478,238 and 6,126,086), and a model with parallel paths of gas (surrounding the liquid capillary) with different velocities to direct the cloud of liquid droplets in a specific direction. A combined cross-flow ultrasonic nebulizer has also been developed (see for example U.S. Pat. No. 4,961,885.)
Other apparatuses and methods for nebulizing or atomizing a liquid solution with gas have been patented including a method of thermal pressurization (U.S. Pat. No. 6,601,776), ultrasonication (U.S. Pat. Nos. 6,555,011; 5,922,247), centrifugal pressurization (U.S. Pat. No. 5,727,541) and specialty nozzles (U.S. Pat. No. 5,269,461). These prior art references support the claimed method when the atomized liquid is combined with a stream of gas moving at substantial velocity.
Prior art patents also include any process which combines an energy field and an oxidant for the treatment of gases, liquids and solids in bulk (see U.S. Pat. Nos. 6,761,863; 6,761,729; 6,555,835; 6,468,433; 6,264,899; 5,765,403; 5,688,378; 4,816,145; 4,265,747); of particular application are advanced oxidation processes which generate hydroxyl radicals (OH.) for oxidative treatment of media (see U.S. Pat. Nos. 6,780,306; 6,630,105; 6,361,697; 6,328,898; 6,264,899; 6,200,466; 6,030,526; 5,512,244; 5,364,537; 5,213,759; 4,849,114).
Liquid treatment systems include compounded reactors geometrically shaped to enhance internally applied UV energy (see U.S. Pat. No. 6,555,011); mixing oxygen, ozone and or hydrogen peroxide into the liquid and contacting the mixture with a free radical inducer (see U.S. Pat. No. 6,361,697); pulse-discharge treatment of oxygen saturated liquid (see U.S. Pat. No. 6,328,898); treatment of water with blackbody radiation (see U.S. Pat. No. 6,200,466); dual annular UV reactor which respectively form ozone from dissolved oxygen and then initiate free radical formation with photolysis of titanium dioxide (see U.S. Pat. No. 6,030,526); dissolution of UV treated humid air, referred to as active air (containing only peroxide and hydroxyl radicals) into a liquid (see U.S. Pat. No. 5,765,403); dissolved oxygen and or photoabsorbers (metals/cations) are irradiated in the liquid being treated; combining ozone and hydrogen peroxide in water to create free radicals (U.S. Pat. No. 5,634,537); dissolved ozone and hydrogen peroxide irradiated with UV light (U.S. Pat. No. 4,849,114); laser disinfection of fluids (U.S. Pat. Nos. 4,816,145; 4,265,747)
Surface decontamination systems include a wand which sprays (using a nozzle) ozone combined with water vapor and hydrogen peroxide onto surfaces which are irradiated by a UV source (either a lamp or a fiber optic cable) on the tip of the wand (see U.S. Pat. No. 6,630,105); a reaction chamber in which the object being treated is heated on a sample stage while being irradiated from above with a UV lamp in an ozone atmosphere; sterilization of an object by exposure to an activated gas medium, composed of irradiated SF6, H2O, O2, H2S, CO, C2H2, Hg, NO, Cl2, N2O, C2H6 or mixtures thereof. (U.S. Pat. No. 5,512,244); ultrasonic nebulization of antiseptic solution (U.S. Pat. No. 5,449,502); and wound treatment with ultrasonic atomization of liquid and laser light (U.S. Pat. No. 6,761,729). A spray device which is based on ICP-MS nebulizer technology also exists for the misting of surfaces with various liquids and gases (U.S. Pat. No. 6,848,633).
Gas purification systems include a method of removing pollutants from flue gas by ozonation of the gas, followed by wet scrubbing, followed by ultra-violet radiation (see U.S. Pat. No. 6,761,863); in this invention, NOx, SOx, and Hg are oxidized by ozone and UV radiation to water soluble species which are removed from the gas phase into the liquid phase. The concentric nebulization of ozone with water is also patent pending for the disinfection of surfaces and treatment of gaseous odors (2004/0096354 A1). Pressurization systems in prior art allow for greater mass transfer of gas into liquids (see U.S. Pat. No. 5,971,368).
Prior art also involves catalysts which can be employed for photolytic production of hydroxyl radicals (see U.S. Pat. No. 6,866,755) include titanium dioxide (TiO2), tungsten oxide (WO3), zinc oxide (ZnO) and other semiconductor catalysts which produce electron hole pairs when irradiated with ultraviolet or ionizing energy; catalysts which generally speed up reaction rates are also applicable.
The method of treatment of media with nebulized oxidant combined with a radiation or energy field and catalyst is unique to the present invention. This new method is designed for superior treatment efficiency due to increased surface area for reaction between oxidants, radiation and constituent requiring oxidation leading to overall more rapid treatment time; it is also a convenient method of generating reactive oxidants for immediate application to a surface without damaging or weakening the surface with direct application of radiation or energy.
The following above-discussed US patents are listed in the following table, each patent hereby incorporated herein by reference:
TABLEPat. No.TITLEISSUE DATE4,265,747Disinfection and purificationMay 19, 1981of fluids using focused laserradiation4,267,976Apparatus for vaporizing andMay 19, 1981atomizing liquids4,344,574Cross-flow nebulizerAug. 17, 19814,575,609Concentric micro-nebulizer forMar. 11, 1986direct sample insertion4,696,719Monomer atomizer forSept. 29, 1987vaporization4,816,145Laser disinfection of fluidsMar. 28, 19894,849,114Oxidation of toxic compoundsJul. 18, 1989in water4,961,885Ultrasonic nebulizerOct. 9, 19904,993,411Ultrasonic oxygen humidifierFeb. 19, 19915,213,759SterilizationMay 25, 19935,269,461Aerosol nozzle systemDec. 14, 19935,364,537Process for the oxidation ofNov. 15, 1994organic micropollutants inwater using the O.sub.3/H.sub.2 O.sub.2 combination5,366,696Oxygenation apparatus forNov. 22, 1994oxygenating a carrier liquid byspraying5,407,604Humidifier using a neubilizerApr. 18, 19955,449,502Sterilizing apparatusSep. 12, 1995utilizing ultrasonic vibration5,512,244Gas sterilizationApr. 30, 19965,688,378Photoassisted oxidation ofNov. 18, 1997species in solution5,727,541Atomization of liquidsMar. 17, 19985,765,403Water treatment method andJun. 16, 1998apparatus5,884,846Pneumatic concentric nebulizerMar. 23, 1999with adjustable andcapillaries5,922,247Ultrasonic device forJul. 13, 1999atomizing liquids5,971,368System to increase the quantityOct. 26, 1999of dissolved gas in a liquidand to maintain the increasedquantity of dissolved gas inthe liquid until utilized6,009,869Supersonic nozzle nebulizerJan. 4, 20006,032,876Apparatus for forming liquidMar. 7, 2000droplets having a mechanicallyfixed inner microtube6,030,526Water treatment andFeb. 29, 2000purification6,126,486Oscillating capillaryOct. 3, 2000nebulizer with electrospray6,166,379Direct injection highDec. 26, 2000efficiency nebulizer foranalytical spectrometry6,200,466Decontamination of water byMar. 13, 2001photolytic oxidation/reductionutilizing near blackbodyradiation6,264,899Method and apparatus for usingJul. 24, 2001hydroxyl to reduce pollutantsin the exhaust gases from thecombustion of a fuel6,328,898Method of and apparatus forDec. 11, 2001forming highly oxidative water6,361,697Decontamination reactor systemMar. 26, 2002and method of using same6,468,433Method for disinfecting liquidsOct. 22, 2002and gases and devices for usethereof6,478,238Miniaturized fluid transferNov. 12, 2002device6,511,050HumidifierJan. 28, 20036,555,011Method for disinfecting andApr. 29, 2003purifying liquids and gasses6,555,835Ultraviolet-ozone oxidationApr. 29, 2003system and method6,630,105Method and apparatus for theOct. 7, 2003gas phase decontamination ofchemical and biological agents6,601,776Liquid atomization methods andAug. 5, 2003devices6,761,729Wound treatment method andJul. 13, 2004device with combination ofultrasound and laser energy6,761,863Process for the removal ofJul. 13, 2004impurities from gas streams6,780,306Electrionic water disinfectionAug. 24, 2004apparatus6,848,633Spray deviceFeb. 1, 20056,866,755Photolytic artificial lungMar. 15, 200520040096354Ozone deodorizing andMay 20, 2004sterilizing method and deviceEP0430904Process for treating wasteNov. 9, 1990water with high concentrationozone water